Phenolysis of diaryl thiolcarbonates and thionocarbonates

Enrique A. Castro, Marjorie Cepeda, Paulina Paveza, José G. Santos

Research output: Contribution to journalArticlepeer-review

8 Citations (Scopus)

Abstract

The phenolysis of phenyl S-4-nitrophenyl thiolcarbonate (1), 4-chlorophenyl S-4-nitrophenyl thiolcarbonate (2), phenyl 4-nitrophenyl thionocarbonate (3), 3-chlorophenyl 4-nitrophenyl thionocarbonate (4) and 3-methoxyphenyl 4-nitrophenyl thionocarbonate (5) are studied kinetically in 44 wt% ethanol-water, at 25.0 °C, ionic strength 0.2 M. The Brøpnsted plots (log kN vs. PKa of phenols) for the reactions of 1 and 2 are linear and those of 3, 4 and 5 are curved. The Brønsted slopes for 1 and 2 are 0.64 and 0.60, respectively, which suggest a concerted mechanism for these reactions. The curved Brønsted plots for the reactions of 3, 4 and 5 show slope values of 1.0, 1.1 and 1.1, respectively, at low pKa and 0.39, 0.28 and 0.34, respectively, at high pK a. The shape and slope values of these Brønsted plots are in accordance with a stepwise mechanism. The reactivity towards phenoxides of the thiocarbonates increases with the increase in the Hammett σ value for the substituents in the non-leaving group. The fact that the phenolysis of 3 is stepwise, whereas that of phenyl 4-nitrophenyl carbonate is concerted can be attributed to the destabilization of the intermediate T-. A similar argument explains the stepwise phenolysis of 3, in contrast to the concerted phenolysis of 1, where there is an additional destabilization of T- caused by the change of the leaving group, from 4-nitrophenoxide in 3 to 4-nitrobenzenethiolate in 1. Thiolcarbonates 1 and 2 in 44 wt% ethanol-water are less reactive towards phenoxide anions (ca. 100-fold) than their corresponding oxycarbonates in water.

Original languageEnglish
Pages (from-to)455-459
Number of pages5
JournalJournal of Physical Organic Chemistry
Volume22
Issue number5
DOIs
Publication statusPublished - May 2009

Keywords

  • Bronsted plots
  • Kinetics
  • Mechanism
  • Phenolysis
  • Thiocarbonates

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

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